Photographic developer compositions containing an antistain agent



3,?ll,5l3 EHQTGGRAKHLC DEVELGEER QBMPUSITKUNS fiflNTAENENG AN ANTEE'TAJNAGENT Richard W. Henri, Rochester, Nil Z, assign-or to Eastman KodakCompany, Rochester, Nit 1., a corporation oi New .llersey No Drawing.Filed Mar. 22, 1961, Ser. No. 97,421

4; (Claims. (Qt. se -s1) This invention relates to photographicdeveloper comnited States Patent positions and more particularly tononstaining photographic developer compositions for black and Whitephotographic emulsions.

When silver halide negative emulsions are developed under conditionshaving considerable solvent action for the silver halide a silver stainor scum tends to be formed. This is particularly so when high speedsilver halide negative emulsions are developed in fine grainphotographic developers which exert considerable solvent action for thesilver halide. The stain is usually metallic by refiected light, andyellow or brown by transmitted light, and may have considerable printingdensity.

While high speed negative silver halide emulsions are most subject tostaining nearly all silver halide emulsions may develop a scum or stainwhen developed in a developer solution having considerable solventaction for the silver halide. Thus, high speed black-and-White silverhalide printing papers tend to stain when developed in a developersolution containing surficient solvent for the silver halide.Accordingly, the utility-of the nonstaining photographic developercompositions of the invention is not restricted to the development of hih speed negative silver halide emulsions.

The silver stain or scum, usually referred to herein simply as stain, ismore likely to be produced in used photographic developer solutions thanin fresh photographic developer solutions and becomes increasinglypronounced with extended developing times. Further, aged silver halidenegative photographic films have a greatertendency to produce silverstain than the corresponding fresh silver halide negative photographicfilms.

It is an object of this invention to prevent the formation of stain whensilver halide emulsions are developed. A particular object is to preventthe formation of stain when silver halide negative emulsions aredeveloped. A further object is to provide photographic developercompositions containing an agent which prevents or greatly reducesstaining. Another object is to provide fine grain photographic developercompositions of improved properties. A further object is to provide aprocess for developing silver halide emulsions, especially silver halideneg tive emulsions, under conditions having considerable solvent actionfor silver halide, in the presence of an agent which effectivelyinhibits staining.

1 have discovered that 2,4-dihydroxybenzophcnone etfectively inhibitsthe formation of the stain or scum which is frequently produced whenhigh speed silver halide negative emulsions are developed underconditions having considerable solvent action for the silver halide.Thus, 2,4-dihydroxybenzophenone inhibits or prevents the formation ofthe stain or scum which is ordinarily produced when high speed silverhalide negative emulsions are developed in fine grain photographicdeveloper solutions which exert considerable solvent action for thesilver halide. The 2,4-dihydroxybenzophenone is normally added to thedeveloper composition. However, it may be incorporated in thephoto-graphic emulsion. As the developer solution becomes exhausted itcan be renewed by the addition of a developer-replenisher solution containing a suitable amount of 2,4-dihydroxybenzophenone.

As indicated hereinbefore, 2,4-dihydroxybenzophenone also efiectivelyinhibits the formation of the stain or scum ddhlfild Patented Dec. 15,1964 that tends to be formed when high speed black-and-white silverhalide printing papers are developed in a developer solution havingconsiderable solvent action for the silver halide. While2,4-dihydroxybenzophenone is of most utility when used in connectionwith the development of silver halide emulsions which are most likely toproduce stain or scum it can be usefully employed in the development ofany silver halide emulsion which tends to produce stain or scum.

The amount of 2,4-dihydroxybenzophenone used varies from about 0.02 toabout 5.0 grams per liter of developing solution. The preferred range isfrom about 0.1 to about 1.0 gram per liter of developing solution. Theaddition of even the lowest concentration of 2,4-dihydroxybenzophenonematerially reduces the intensity of the stain. Higher concentrationsfrequently entirely prevent staining.

2,4-dihydroxybenzophenone has powerful antistain action, has suitablephysical properties, may be employed in low concentrations and haslittle sensitometnic etfefi.

Illustrative of the silver halide negative emulsions that can beadvantageously developed in the presence of 2,4- dihydroxybenzophenoneare the emulsions present in Ko dak Panatomic-X, Kodak Verichrome Pan,Kodak Plus- X Pan, Kodak Tri-X Pan, Kodak Royal-X Pan, Ansco All-WeatherPan, Ansco Super Hypan, Ansco Superpan Press, Gevaent X-L Pan, llfordHP-S, llford HPS and Ilford FP-B photographic film. All of thesephotographic films have negative speed silver bromoiodide emulsions.They are merely illustrative and not limitative of the photographicfilms that can'be developed with advantage in the presence of2,4-dil1ydroXybenzophenone.

Printing papers containing high speed silver bromoiodide emulsions areillustrative of the printing papers that can be developed with advantagein the presence of 2,4-dihydroxybenzophenone.

The photographic films mentioned hereinbefore and other brands ofphotographic film corresponding thereto, have high speed silver halidenegative emulsions even though the various emulsions vary greatly intheir speed ratings.

The use of 2,4-dihydroxybenzophenone as an antistaining agent is notrestricted to any particular photographic developer or class ofphotographic developers. So far as I am aware it can be used with miy ofthe known photographic developers. The photographic developer solutioncan have the agents usually present therein, e.g. photographicdeveloper, a preservative such as sodium sulfite and an alkaline agentsuch as sodium hydroxide or sodium carbonate. Other ingredients such aspotassium bromide, benzotriazole or toners, for example, can also bepresent. Hydroquinone, pmamethylaminophenol sulfate,paraphenylenediamine, p-aminophenol, l-phenyl- Z-pyrazolidone,4,4-dimethyl-l-phenyl-3-pyrazolidone, lphenyl 4 ethyl 3 pyrazolidone,2,4 diaminophenol and pyrogallol are illustrative of the developingagents that can be employed. Mixtures of developing agents such ashydroquinone and paramethylaminophenol sulfate, and4,4-dimethyl-l-phenyl-3-pyrazolidone and hydro quinone, for example, canbe employed.

Sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, sodiumchloride, ammonium chloride, ethylene diamine, 1,3,5-triaminobenzene,ethanolarnine, diethanolamine, sodium thiosulfate and sodium sulfite areillustrative of the silver halide solvents that can be presout duringthe development step.

The following examples illustrate my invention.

EXAMPLE 1 Strips of Kodak Royal-X Pan Film which had been incubated forone Week at F. were tested in Kodak Developer DK SO and in thisdeveloper having varying amounts of 2,4-dihydroxybenzophenone (0.1 and0.5

9 gram per liter) therein. These developer solutions are referred to as1, 2 and 3 for purpose of reference. The strips were developed in largetest tubes of developer solution at 68 F. for 10 minutes. As each stripwas removed firom the developer solution a portion of the strip waswiped with the fingers in order that the stained area could be morereadily detected and compared with a clear area. The strips were thenimmersed in a stop bath, fixed, and washed with water. The developersolution containing no 2,4-dihydroxybenzophenone produced an intensestain whereas the developer solutions containing 2,4-dihydroxybenzophenone produced little or no stain.

The results obtained are tabulated hereinafter.

A solution of Kodak Developer DK-50 containing 0.2 gram of2,4-dihydroxybenzophenone per liter of developer solution was exhaustedby the processing of successive rolls of Kodak Verichrome Pan Filmhaving 80 square inches of emulsion per roll. After each roll of filmwas developed 11 cc. of Kodak Replenisher DK- 50R solution, modified bythe addition of 0.5 gram of 2,4- dihydroxybenzophenone per liter ofsolution, were added to the developer solution. No stain was encounteredat any stage of the processing, even after developing the equivalent of400 rolls per gallon of the starting developer solution. By contrast,the unmodified Kodak Developer DK-50 and unmodified Kodak ReplenisherDK-SOR used as a control produced high dichroic silver stain.

Kodak Developer DK-50 and Kodak Replenisher DK- 50R, and their use, aredescribed, for example, in the Kodak Data Book, th edition (first 1960printing), entitled Processing Chemicals and Formulas for Blackand-WhitePhotography.

The 2,4-dihydroxybenzophenone antistaining or antiscumming agent of myinvention can be added to combined developing and fixing compositionsand to combined developing and stabilizing compositions. Thus,2,4-dihydroxybenzophenone may be added to the monobath compositionsdisclosed, for example, in Haist et a1. U.S. Patent 2,875,048, issuedFebruary 24, 1959, Dreywood US. Patent 2,525,532, issued October 10,1959, King US. Patent 2,397,016, issued March 19, 1946, Goldhammer etal. US. Patent 2,782,120, issued February 19, 1957, and Goldharnmer U.S.Patents 2,782,121 and 2,901,350, issued February 19, 1957, and August25, 1959, respectively. Some of these combined developer and fixer ordeveloper and stabilizer compositions can be prepared in dry form formaking working solutions.

Kodak Developer DK-50 contains the following ingredients per liter ofsolution.

Grams Paramethylaminophenol sulfate 2.5 Sodium sulfite, desiccated 30.0Hydroquinone 2.5 Sodium bisulfite 15.0 Sodium metaborate 10.0 Potassiumbromide 0.5

Other photographic developers that can be modified with2,4-dihydroxybenzophenone include Kodak Developer D-23, Kodak DeveloperD-25, Kodak Developer D76, Kodak Developer SD-21 and Kodak DeveloperSD-28, for example. These developers are merely illustrative and notlimitative of the developers that can be modified with2,4-dihydroxybenzophenone.

The 2,4-dihydroxybenzophenone antista'ining agent of my invention may beincorporated in stable, dry, single powder photographic developercompositions of the types described, for example, by Kridel et al. US.Patents 2,666,702 and 2,666,703, issued January 19, 1954, Wiitala et al.US. Patents 2,682,464 and 2,682,465, issued June 29, 1954, Henn et al.US. Patent 2,685,513, issued August 3, 1954, and Baxendale et al. US.Patent 2,816,- 026, issued December 10, 1957.

Representative stable, dry, single powder photographic developercompositions containing 2,4-dihydroxybenzophenone are set forthhereinafter.

EXAMPLE 3 Grams Elon 2.0 Hydroquinone 8.0 Sodium sulfite (desiccated)90.0 Sodium carbonate monohydrate 52.5 Potassium bromide 5.0 Boricanhydride 1.6 Phthalic anhydride 0.16 2,4-dihydroxybenzophenone 1 .0

EXAMPLE 4 Elon 2.5 Sodium sulfite (desiccated) 30.0 Hydroquinone 2.5Sodium metaborate (10% H O) 10.5 Potassium bromide 0.5 Boric anhydride0.5 Phthalic anhydride 0.05 2,4-dihydroxybenzophenone 0.5

EXAMPLE 5 Elon 2.2 Anhydrous sodium sulfite 96.0 Hydroquinone 8.8 Sodiumcarbonate monohydrate 57.5 Potassium bromide 5.0 Metaboric acid 3.42,4-dihydroxybenzophenone 0.1

EXAMPLE 6 Elon 2.5 Anhydrous sodium sulfite 30.0 Hydroquinone 2.5 Sodiummetaborate (10% H O) 10.5 Potassium bromide 0.5 Metaboric acid 4.72,4-dihydroxybenzophenone 0.5

EXAMPLE 7 Elon 3.0 Sodium sulfite 45.0 Hydroquinone 12.0 Sodiumcarbonate monohydrate 80.0 Potassium bromide 0.6 5-methyl benzotriazole0.06 Metaboric acid 1.4 2,4-dihydroxybenzophenone 1.0

The foregoing stable, dry, single powder photographic developercompositions are merely illustrative and not limitative.

The compositions for Kodak Developer SD-21 and Kodak Developer SD-28 aregiven hereinafter.

Kodak Developer SD-21 H 0 to make 1 liter.

The compositions for Kodak Developer D-23, Kodak Developer D-25 andKodak Developer 13-76 are given hereinafter.

Kodak Developer D23 Water, about 125 F. (50 C.) cc 750 Elon grams 7.5Sodium sulfite, desiccated do 100.0 Cold water to make 1.0 liter.

Dissolve chemicals in the order given.

Kodak Developer D-25 Water, about 125 F. (50 C.) cc 750 Elon grams 7.5Sodium sulfite, desiccated do 100.0 Sodium bisulfite do 15.0 Cold waterto make 1.0 liter.

Dissolve chemicals in the order given.

Kodak Developer D-76 Water, about 125 F. 50 c. cc 750 Elon grams 2.0Sodium sulfite, desiccated do 100.0 Hydroquinone do 5.0 Borax, granularH. do 2.0 Water to make 1.0 liter.

Dissolve chemicals in the order given,

I have also discovered that m-cresol, ortho phenylphenol,pentachlorophenol and thiobenzanilide possess antistaining activity.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spinit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

I claim: I

1. A photographic developing solution containing an organic silverhalide photographic developer selected-from the group consisting ofhydroquinone, 'paramethylaminophenol sulfate, paraphenylenediamine,p-aminophenol, 2,4-diaminophenol, pyrogallol and a 1-phenyl-3 pyrazolidone, a silver halide solvent in sufficient amount to exertconsiderable solvent action for silver halide and from about 0.02toabout 5.0 grams of 2,4-dihydroxy benzophenone per liter of thedeveloping solution.

2. A photographic developing solution containing an organic silverhalide photographic developer selected from the group consisting ofhydroquinone, paramethylaminophenol sulfate, paraphenylenediamine,p-aminophenol, 2,4-diaminophenol, pyrogallol and a l-phenyl 3pyrazolidone, a silver halide solvent in sufficient amount to exertconsiderable solvent action for silver halide and from about 0.1 toabout 1.0 gram of 2,4-dihydroxybenzophenone per liter of the developingsolution.

3. As anew photographic developer composition, an

. 6 aqueous solution comprising an alkaline material, an organic silverhalide photographic developer selected from the group consisting ofhydroquinone, paramethylaminophenol sulfate, paraphenylenediamine,p-aminophenol, 2,4-diamino henol, pyrogallol and a l-p-henyl 3pyrazolidone, sodium sulfite in sufficient amount to exert considerablesolvent action for silver halide and from about 0.02 to about 5.0 gramsof 2,4-dihydroxybenzophenone per liter of the developer solution.

4. As a new photographic developer composition an aqueous solutioncomprising paramethylaminophenol sulfate, an alkaline material, sodiumsulfite in suflicient amount to exert considerable action for silverhalide and from about 0.02 to about 5.0 grams of2,4-dihydroxybenzophenone per liter of the developer solution.

5. in the process for developing an exposed high speed silver halideemulsion with an organic silver halide photographic developer selectedfrom the group consisting of hydroquinone, paramethylaminophenolsulfate, paraphenylenediamine, p-aminophenol, 2,4-diaminophenol,pyrogallol and a l-phenyl-S-pyrazolidone, under conditions which exertconsiderable solvent action for the silver halide the improvement whichconsists in carrying out the developing reaction in the presence of fromabout 0.02 to about 5.0 grams of 2,4-dihydroxybenzophenone per liter ofthe developer solution.

6. In the process for developing an exposed high speed silver halidenegative emulsion with an organic silver halide photographic developerselected from the group fconsisting of hydroquinone,paramethylaminophenol sul- Grams Paramethylaminophenol sulfate 2.5Sodium sulfite, desiccated 30.0 Hydroquinone 2.5 Sodium bisulfite 15.0Sodium metaborate 10.0 Potassium bromide 0.5 2,4-dihydroxybenzophenone0.02 to 5.0

8. A photographic developer solution containing as its essentialingredients for one liter of developer solution:

Grams Paramethylaminophenol sulfate 2.5' Sodium sulfite, desiccated 30.0Hydroquinone c 2.5 Sodium bisulfite 15.0 Sodium metaborate 10.0Potassium bromide 0.5 2,4-dihydroxybenzophenone 0.1 to 1.0

References Cited in the file of this patent UNITED STATES PATENTS2,279,514 Ham et al Apr. 14, 1942 2,682,559 Stanley June 29, 19542,983,604 Duffy et a1. May 9, 1961 OTHER REFERENCES

1. A PHOTOGRAPHIC DEVELOPING SOLUTION CONTAINING AN ORGANIC SILVERHALIDE PHOTOGRAPHIC DEVELOPER SELECTED FROM THE GROUP CONSISTING OFHYDROQUINONE, PARAMETHYLAMINOPHENOL SULFATE, PARAPHENYLENEDIAMINE,P-AMINOPHENOL, 2,4-DIAMINOPHENOL,PYROGALLOL AND 2 1-PHENYL-3-PYRAZOLIDONE, A SILVER HALIDE SOLVENT IN SUFFICIENT AMOUNT TO EXERTCONSIDERABLE SOLVENT ACTION FOR SILVER HALIDE AND FROM ABOUT 0.02 TOABOUT 5.0 GRAMS OF 2,4-DIHYDROXYBENZOPHENONE PER LITER OF THE DEVELOPINGSOLUTION.